JP7226446B2 - sintered body - Google Patents

Description

The present disclosure relates to sintered bodies, powders, and methods of making powders. This application claims priority based on Japanese Patent Application No. 2018-134072 filed on July 17, 2018. All the contents described in the Japanese patent application are incorporated herein by reference.

One of the important properties required for cutting tools is wear resistance. Therefore, efforts are being made to develop materials for cutting tools that have superior wear resistance.

Japanese Patent Application Laid-Open No. 2016-037648 (Patent Document 1) describes aluminum and nitrogen as hard materials capable of obtaining a sintered body having excellent wear resistance when used as a material for the sintered body. , at least one selected from the group consisting of titanium, chromium and silicon, and having a cubic rocksalt structure.

JP 2016-037648 A

A sintered body according to an aspect of the present disclosure is
Derived from a powder containing either or both of a nitride and an oxynitride of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table equipped with materials,
In the powder-derived material, the value of the ratio y1/x1 between the atomic ratio x1 of the metallic element and the atomic ratio y1 of the nonmetallic element is greater than 1,
The powder-derived material is a sintered body having a cubic crystal structure.

The powder according to one aspect of the present disclosure is
containing either or both nitrides and oxynitrides of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table;
The value of the ratio y1/x1 between the atomic ratio x1 of the metallic element and the atomic ratio y1 of the nonmetallic element is greater than 1,
It is a powder made of a material with a cubic crystal structure.

A method for producing a powder according to one aspect of the present disclosure includes:
A method for producing the powder described above,
Preparing a first particle group containing particles of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table;
and processing the first particle group by an impact compression method in a nitrogen atmosphere to produce the powder.

[Problems to be Solved by the Present Disclosure]
Although the sintered body produced using the hard material of Patent Document 1 has good wear resistance, further improvement in wear resistance is required.

Therefore, the object of the present invention is to provide a sintered body having excellent wear resistance, a powder capable of obtaining a sintered body having excellent wear resistance when used as a material for the sintered body, and a powder containing the powder. The object is to provide a manufacturing method.
[Effect of the present disclosure]
According to the above aspect, the sintered body having excellent wear resistance, the powder capable of obtaining the sintered body having excellent wear resistance when used as a material for the sintered body, and the powder It becomes possible to provide a manufacturing method.

[Description of Embodiments of the Present Disclosure]
First, the embodiments of the present disclosure are listed and described.

(1) A sintered body according to an aspect of the present disclosure includes nitriding of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements, and Group 6 elements of the periodic table. A powder-derived material containing either or both of a substance and an oxynitride,
In the powder-derived material, the value of the ratio y1/x1 between the atomic ratio x1 of the metallic element and the atomic ratio y1 of the nonmetallic element is greater than 1,
The powder-derived material is a sintered body having a cubic crystal structure.

A sintered body according to an aspect of the present disclosure can have excellent wear resistance.
(2) The value of y1/x1 is preferably 1.1 or more and 1.3 or less. According to this, the wear resistance of the sintered body is further improved.

(3) Preferably, the sintered body further contains one or both of Al and Si. According to this, the wear resistance of the sintered body is further improved.

(4) The sintered body further contains at least one binder compound in a total of 0.5% by volume or more and 50% by volume or less,
The binder compound contains at least one second metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table, and at least one of carbon, nitrogen and oxygen. consists of
In the binder compound, it is preferable that the value of the ratio x2/y2 of the atomic ratio x2 of the metallic element and the atomic ratio y2 of the nonmetallic element is 1 or more.

The binder compound acts as a binder phase in the sintered body. Therefore, since the strength of the sintered body containing the binder compound is improved, the sintered body can have even better wear resistance.

(5) The value of the ratio x2/y2 is preferably 1.04 or more and 1.06 or less. According to this, the sintered body can have even better wear resistance.

(6) The sintered body preferably further contains cubic boron nitride in an amount of 10% by volume or more and 97% by volume or less. Since cubic boron nitride has extremely high hardness, when the sintered body contains cubic boron nitride, the hardness of the sintered body increases and the abrasion resistance of the sintered body improves.

(7) The powder according to one aspect of the present disclosure is a nitride of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements, and Group 6 elements of the periodic table, and containing either or both of the oxynitrides,
The powder is made of a material having a cubic crystal structure in which the ratio y1/x1 of the atomic ratio x1 of the metallic element to the atomic ratio y1 of the nonmetallic element is greater than 1.

When the powder according to one aspect of the present disclosure is used as a material for a sintered body, a sintered body having excellent wear resistance can be obtained.

(8) The value of y1/x1 is preferably 1.1 or more and 1.3 or less. When such a powder is used as a material for a sintered body, a sintered body having excellent wear resistance can be obtained.

(9) A method for producing a powder according to an aspect of the present disclosure is the method for producing a powder according to (7) or (8) above,
Preparing a first particle group containing particles of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table;
and processing the first particle group by an impact compression method in a nitrogen atmosphere to produce the powder.

According to the powder manufacturing method according to one aspect of the present disclosure, powder having a cubic crystal structure can be obtained.

[Details of the embodiment of the present disclosure]
Specific examples of the sintered body, the powder, and the method for producing the powder according to an embodiment of the present disclosure are described below. In the present specification, when a compound is represented by a chemical formula, if the atomic ratio is not particularly limited, it includes any conventionally known atomic ratio, and is not necessarily limited only to the stoichiometric range. For example, even if it is simply described as "TiN", the atomic ratio of "Ti" and "N" is not limited to 50:50, but includes all conventionally known atomic ratios.

<Embodiment 1: Powder>
The powder according to one embodiment of the present disclosure is a nitride and acid of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table. It is made of a material containing either one or both of nitrides, having a ratio y1/x1 of the atomic ratio x1 of the metallic element to the atomic ratio y1 of the nonmetallic element greater than 1, and having a cubic crystal structure.

In the present embodiment, Group 4 elements of the periodic table included in the first metal element include, for example, titanium (Ti), zirconium (Zr), and hafnium (Hf), and Group 5 elements include, for example, vanadium. (V), niobium (Nb) and tantalum (Ta), and Group 6 elements include, for example, chromium (Cr), molybdenum (Mo) and tungsten (W).

Examples of nitrides of the first metal element include titanium nitride (TiN), zirconium nitride (ZrN), hafnium nitride (HfN), vanadium nitride (VN), niobium nitride (NbN), tantalum nitride (TaN), and chromium nitride. (Cr ₂ N), molybdenum nitride (MoN), tungsten nitride (WN).

Examples of the oxynitride of the first metal element include titanium oxynitride (TiON), zirconium oxynitride (ZrON), hafnium oxynitride (HfON), vanadium oxynitride (VON), niobium oxynitride (NbON), and oxynitride. Tantalum (TaON), chromium oxynitride (CrON), molybdenum oxynitride (MoON), and tungsten oxynitride (WON) can be mentioned.

The powder may be composed of one of the nitride and oxynitride of the first metal element, or may be composed of a combination of two or more. The total content of the nitride and oxynitride of the first metal element in the powder is preferably 90% by mass or more, more preferably 95% by mass or more, and 100% by mass with respect to the total mass of the powder. is most preferred.

The powder can contain either one or both of Al and Si. Al and Si are preferably dissolved in the powder. The content of Al in the powder is preferably 1 atomic % or more and 25 atomic % or less, more preferably 3 atomic % or more and 15 atomic % or less. The content of Si in the powder is preferably 1 atomic % or more and 25 atomic % or less, more preferably 3 atomic % or more and 15 atomic % or less.

The powder may contain unavoidable impurities. The content of inevitable impurities is preferably 0% by mass or more and less than 10% by mass, more preferably 0% by mass or more and less than 5% by mass, relative to the total mass of the powder.

The content of metal elements in the powder can be measured by ICP analysis of the powder. The content of nonmetallic elements (nitrogen and oxygen) in the powder can be measured by gas analysis of the powder. When the powder is present as a powder-derived material in the sintered body, the sintered body is pulverized with a pulverizer (eg, vibrating disc mill, "RS200" manufactured by Retsch), and the powder is subjected to ICP analysis and gas analysis. conduct.

As an ICP emission spectrometer, for example, "ICPS-8100" manufactured by Shimadzu Corporation can be mentioned. As a gas analyzer, for example, "EMG950" manufactured by Horiba, Ltd. can be cited.

In the powder, the value of the ratio y1/x1 between the atomic ratio x1 of the metallic element and the atomic ratio y1 of the nonmetallic element is greater than one. Here, the atomic ratio x1 of the metal elements means the ratio of the total number of atoms of the metal elements to the total number of atoms composing the powder, and the unit can be expressed in atomic %. Further, the atomic ratio y1 of the non-metallic elements means the ratio of the total number of atoms of the non-metallic elements to the total number of atoms constituting the powder, and the unit can be expressed in atomic %. Therefore, in the powder of the present embodiment, the number of atoms of the nonmetallic element is larger than the number of atoms of the metal element. In this specification, the term "nonmetallic element" refers to hydrogen, helium, neon, argon, krypton, xenon, radon, fluorine, chlorine, bromine, iodine, astatine, oxygen, sulfur, selenium, tellurium, nitrogen, phosphorus. , arsenic, antimony and carbon. In addition, the term “metallic element” refers to elements other than the aforementioned “nonmetallic element”.

In the powder, when the atomic ratio y1 of the non-metallic element is greater than the atomic ratio x1 of the metallic element, the hardness of the powder increases, and when the powder is used as a material for the sintered body, sintering with excellent wear resistance is achieved. you can get a body Although the reason for this is not clear, if the atomic ratio y1 of the non-metallic element in the powder is greater than the atomic ratio x1 of the metallic element, the covalent bond between the two nitrogen atoms and the bond between the nitrogen atom and the oxygen atom are formed in the powder. and the covalent bond between two oxygen atoms. For this reason, it is inferred that the hardness of the powder increases.

The atomic ratio x1 of the metal element in the powder can be measured by analysis using ICP emission spectrometry. Specifically, an arbitrary 1 g is selected from the powder for measurement pulverized, and this is divided by the number of metal elements to be analyzed. In each divided powder, among the metal elements to be analyzed, atoms of one metal element Measure the ratio. For example, when measuring two kinds of metal elements, 1 g of the powder for measurement is divided into two. When the two divided powders are divided powder A and divided powder B, the atomic ratio of one metal element in divided powder A is obtained, and the atomic ratio of another metallic element in divided powder B is obtained.

The above measurement operation is performed 10 times for each element, and the average value of the values obtained 10 times is taken as the atomic ratio of one kind of metal element in the powder. The sum of the atomic ratios of all the analyzed metal elements is calculated, and this value is taken as the atomic ratio of the metal elements in the powder. As an ICP emission spectrometer, for example, "ICPS-8100" (trade name) manufactured by Shimadzu Corporation can be used.

The atomic ratio x1 of the metal element in the powder is preferably 43.48 atomic % or more and 48.39 atomic % or less, more preferably 44.12 atomic % or more and 46.88 atomic % or less.

The atomic ratio y1 of the non-metallic elements in the powder can be measured by analysis using a gas analysis measurement method. Specifically, an arbitrary 1 g of powder is selected from the pulverized powder, divided by the number of non-metallic elements to be analyzed, and in each divided powder, among the non-metallic elements to be analyzed, Measure the atomic ratio. For example, when measuring two kinds of nonmetallic elements, 1 g of the powder for measurement is divided into two. When the two divided powders are divided powder 1 and divided powder 2, the atomic ratio of one non-metallic element is obtained for divided powder 1, and the atomic ratio of another non-metallic element is obtained for divided powder 2. .

The above measurement operation is performed 10 times for each element, and the average value of the values obtained 10 times is taken as the atomic ratio of one kind of non-metallic element in the powder. The sum of the atomic ratios of all analyzed non-metallic elements is calculated, and this value is taken as the atomic ratio of the non-metallic elements in the powder. As a gas analyzer, for example, "EMG950" manufactured by Horiba, Ltd. can be used.

The atomic ratio y1 of the nonmetallic elements in the powder is preferably 56.52 atomic % or more and 51.61 atomic % or less, more preferably 55.88 atomic % or more and 53.13 atomic % or less.

The ratio y1/x1 between the atomic ratio x1 of the metallic element and the atomic ratio y1 of the nonmetallic element is preferably greater than 1 and 1.33 or less, more preferably 1.1 or more and 1.3 or less, and 1.13 or more. 1.27 or less is more preferable.

The powder has a cubic crystal structure. The cubic crystal structure is a crystal structure represented by rock salt (sodium chloride), and two different types of face-centered cubic lattices are shifted by half the length of the cubic lattice in the direction of the cubic lattice of the unit. It is a structure that is combined with each other. Since the cubic crystal structure has high hardness, the use of a powder having a cubic crystal structure as a material for the sintered body makes it possible to obtain a sintered body having excellent wear resistance.

It is possible to confirm that the powder contains a cubic crystal structure by performing qualitative analysis by comparing the XRD diffraction pattern with the ICDD database. Examples of the X-ray diffraction device include "miniflex 600" manufactured by RIGAKU.

Preferably, 90% by volume or more of the powder consists of a material having a cubic crystal structure, and more preferably 100% by volume, that is, all of the powder consists of a material having a cubic crystal structure.

<Embodiment 2: Sintered body>
A sintered body according to an embodiment of the present disclosure is a sintered body containing a powder-derived material derived from the powder according to the first embodiment. Since the sintered body contains a powder-derived material derived from powder with high hardness, it has excellent wear resistance.

In this specification, the powder-derived material means a component derived from the powder of Embodiment 1 that is present in the sintered body when the powder of Embodiment 1 is used to produce the sintered body. . The constituents of the powder and the proportions of each constituent are maintained after sintering. Therefore, the powder and the powder-derived material in the sintered body obtained by sintering the powder have the same constituents and the same ratio of the constituents.

The sintered body can be composed only of powder-derived materials. That is, the content of the powder-derived material in the sintered body can be 100% by volume. In addition, the sintered body can have a powder-derived material content of, for example, 3% by volume or more and 99.5% by volume or less. In this case, in addition to the powder-derived material, other ingredients such as binder compounds, cubic boron nitride, etc. may also be included. The content of these other components in the sintered body can be, for example, 0.5% by volume or more and 97% by volume or less.

Preferably, the sintered body further contains either one or both of Al and Si. Al and Si are preferably dissolved in the sintered body. Al and Si are preferably dissolved in the powder-derived material. According to this, the wear resistance of the sintered body is further improved. The content of Al in the sintered body is preferably 1 atomic % or more and 25 atomic % or less, more preferably 3 atomic % or more and 15 atomic % or less. The content of Si in the sintered body is preferably 1 atomic % or more and 25 atomic % or less, more preferably 3 atomic % or more and 15 atomic % or less.

The respective contents of Al and Si in the sintered body can be measured by analysis using ICP emission spectrometry. A specific measuring method is the same as the method for measuring the atomic ratio of metal elements in the powder in the first embodiment.

The sintered body further contains at least one second metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table, and at least one of carbon, nitrogen and oxygen. It is preferred to include at least one binder compound consisting of Here, the elements of Group 4, Group 5, and Group 6 of the periodic table included in the second metal element include, for example, titanium (Ti), zirconium (Zr), and hafnium (Hf). Group 5 elements include, for example, vanadium (V), niobium (Nb) and tantalum (Ta), and group 6 elements include, for example, chromium (Cr), molybdenum (Mo) and tungsten (W).

The binder compound in the sintered body exists at the interface between adjacent powder-derived materials and plays the role of a binder phase. Since the binder phase can firmly bind the powder-derived materials together, the strength of the sintered body can be improved, and the sintered body can have even better wear resistance.

In addition, since the sintered body contains the binder phase, the sintered body can have properties due to the binder phase in addition to the properties of the powder-derived material. Therefore, by appropriately adjusting the composition of the binder phase, the sintered body can flexibly meet various needs for various cutting conditions.

Examples of binder compounds (carbides) composed of the second metal element and carbon include titanium carbide (TiC), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), Mention may be made of tantalum carbide (TaC), chromium carbide ( _Cr3C2 ), molybdenum carbide ( _MoC ), tungsten carbide (WC).

Examples of binder compounds (nitrides) composed of the second metal element and nitrogen include titanium nitride (TiN), zirconium nitride (ZrN), hafnium nitride (HfN), vanadium nitride (VN), and niobium nitride (NbN). , tantalum nitride (TaN), chromium nitride ( _Cr2N ), molybdenum nitride (MoN), tungsten nitride (WN), titanium zirconium nitride (TiZrN), titanium hafnium nitride (TiHfN), titanium vanadium nitride (TiVN), titanium niobium nitride (TiNbN), titanium tantalum nitride (TiTaN), titanium chromium nitride (TiCrN), titanium molybdenum nitride (TiMoN), titanium tungsten nitride (TiWN), zirconium hafnium nitride (ZrHfN), zirconium vanadium nitride (ZrVN), zirconium niobium nitride ( ZrNbN), zirconium tantalum nitride (ZrTaN), zirconium chromium nitride (ZrCrN), zirconium molybdenum nitride (ZrMoN), zirconium tungsten nitride (ZrWN), hafnium vanadium nitride (HfVN), hafnium niobium nitride (HfNbN), hafnium tantalum nitride (HfTaN) ), hafnium chromium nitride (HfCrN), hafnium molybdenum nitride (HfMoN), hafnium tungsten nitride (HfWN), vanadium niobium nitride (VNbN), vanadium tantalum nitride (VTaN), vanadium chromium nitride (VCrN), vanadium molybdenum nitride (VMoN) , vanadium tungsten nitride (VWN), niobium tantalum nitride (NbTaN), niobium chromium nitride (NbCrN), niobium molybdenum nitride (NbMoN), niobium tungsten nitride (NbWN), tantalum chromium nitride (TaCrN), tantalum molybdenum nitride (TaMoN), nitriding Mention may be made of tantalum tungsten (TaWN), chromium molybdenum nitride (CrMoN), chromium tungsten nitride (CrWN), molybdenum chromium nitride (MoWN).

Examples of binder compounds (oxides) composed of the second metal element and oxygen include titanium oxide (TiO ₂ ), zirconium oxide (ZrO ₂ ), hafnium oxide (HfO ₂ ), and vanadium oxide (V ₂ O ₅ ). , niobium oxide (Nb ₂ O ₅ ), tantalum oxide (Ta ₂ O ₅ ), chromium oxide (Cr ₂ O ₃ ), molybdenum oxide (MoO ₃ ), tungsten oxide (WO ₃ ).

Examples of binder compounds (carbonitrides) composed of the second metal element, carbon, and nitrogen include titanium carbonitride (TiCN), zirconium carbonitride (ZrCN), and hafnium carbonitride (HfCN).

Examples of the binder compound (oxynitride) composed of the second metal element, oxygen, and nitrogen include titanium oxynitride (TiON), zirconium oxynitride (ZrON), hafnium oxynitride (HfON), vanadium oxynitride (VON), ), niobium oxynitride (NbON), tantalum oxynitride (TaON), chromium oxynitride (CrON), molybdenum oxynitride (MoON), and tungsten oxynitride (WON).

One type of binder compound may be used, or two or more types may be used in combination.
The content of the binder compound in the sintered body is preferably 0.5% by volume or more and 50% by volume or less, more preferably 15% by volume or more and 45% by volume or less, and even more preferably 30% by volume or more and 40% by volume or less.

In the binder compound, the value of the ratio x2/y2 between the atomic ratio x2 of the metallic element and the atomic ratio y2 of the nonmetallic element is preferably 1 or more. Here, the atomic ratio x2 of the metal elements means the ratio of the total number of atoms of the metal elements to the total number of atoms constituting the binder compound. Further, the atomic ratio y2 of the nonmetallic elements means the ratio of the total number of atoms of the nonmetallic elements to the total number of atoms constituting the binder compound. That is, in the binder compound of the present embodiment, the atomic ratio of the metallic element is preferably the same as or greater than the atomic ratio of the non-metallic element. The “metallic element” and the “nonmetallic element” are as described in the first embodiment.

In the binder compound, if the atomic ratio of the metallic element is the same as or greater than the atomic ratio of the non-metallic element, the excessive metallic element reacts with the excessive non-metallic element in the powder-derived material. , the bond is strengthened and the chipping resistance is improved.

The atomic ratios x2 and y2 of the metallic element and the non-metallic element in the binder compound can be measured by the following method. By STEM observation, the powder-derived material and the binder compound are separated by elemental mapping. When the powder-derived material and the binder compound use the same elements, the crystal structure is identified from the electron diffraction pattern to identify the binder compound portion. Quantitative analysis is performed by point analysis of the binder compound portion. Twenty points are measured by point analysis, and the average values are defined as x2 and y2, respectively. Examples of STEM include "JEM-ARM300F" manufactured by JOEL.

The atomic ratio x2 of the metal element in the binder compound is preferably 50 atomic % or more and 53 atomic % or less, more preferably 51 atomic % or more and 52 atomic % or less.

The atomic ratio y2 of the nonmetallic element in the binder compound is preferably 47 atomic % or more and 50 atomic % or less, more preferably 48 atomic % or more and 49 atomic % or less.

The value of the ratio x2/y2 between the atomic ratio x2 of the metallic element and the atomic ratio y2 of the nonmetallic element is preferably 1 or more and 1.13 or less, more preferably 1.02 or more and 1.10 or less, and 1.04 or more and 1.04 or more. 0.06 or less is more preferable.

The sintered body preferably further contains cubic boron nitride in an amount of 10% to 97% by volume, more preferably 30% to 65% by volume, and more preferably 45% to 55% by volume. preferable.

Since cubic boron nitride has extremely high hardness, when the sintered body contains cubic boron nitride, the hardness of the sintered body increases and the abrasion resistance of the sintered body improves.

The sintered body of this embodiment can be used as a material for tools. Since the sintered body is excellent in wear resistance, a tool using the sintered body is also excellent in wear resistance.

Examples of tools include cutting tools, grinding tools, wear-resistant tools, tools for friction stir welding, and the like. Examples of cutting tools include drills, end mills, indexable cutting inserts for milling, indexable cutting inserts for turning, metal saws, gear cutting tools, reamers, and taps. The cutting tool may be entirely composed of the sintered body of the present embodiment, or part thereof (for example, a cutting edge portion) may be composed of the sintered body of the present embodiment.

When the entire cutting tool is made of the sintered body of the present embodiment, the cutting tool can be produced by processing the sintered body into a desired shape. Processing of the sintered body can be performed, for example, by laser or wire discharge. Further, when a part of the cutting tool is made of the sintered body of the present embodiment, the cutting tool can be manufactured by bonding the sintered body to a desired position of the base body constituting the tool. The method for joining the sintered body is not particularly limited, but from the viewpoint of suppressing the separation of the sintered body from the base, it is necessary to firmly bond the base and the sintered body between the base and the sintered body. It is preferable to interpose a bonding layer of

<Embodiment 3: Method for producing powder>
A powder manufacturing method according to an embodiment of the present disclosure includes particles of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements, and Group 6 elements of the periodic table A step of preparing a first particle group containing hereinafter, “powder preparation step”).

(First particle group preparation step)
In the first particle group preparation step, a first particle group containing particles of at least one first metal element selected from the group consisting of elements of Group 4, Group 5 and Group 6 of the periodic table prepare. These particles preferably have an average particle size of 2 μm or less, more preferably 1 μm or less. As used herein, "average particle size" means a value measured by a particle size distribution analyzer such as Microtrac.

The first particle group serves as a powder raw material. A metal element forming the powder is supplied only from the first particle group. Therefore, the content ratio of each metal element in the first particle group must be the same as the content ratio of each metal element in the target powder. On the other hand, nitrogen in the powder is supplied from the atmosphere (nitrogen atmosphere). Therefore, the nitrogen content ratio in the first particle group does not need to be the same as the nitrogen content ratio in the powder. In addition, oxygen in the powder is supplied from the atmosphere (oxygen-nitrogen mixed gas) like nitrogen. Therefore, the oxygen content ratio in the first particle group does not need to be the same as the oxygen content ratio in the powder.

The first particle group comprises particles of at least one first metal element selected from the group consisting of elements of Group 4, Group 5, and Group 6 of the periodic table in an organic solvent such as ethanol. It can be obtained by sonicating or pulverizing and mixing with a bead mill and drying the obtained slurry with a dryer or the like.

(Powder production process)
Next, in the powder production step, the first particle group is processed by an impact compression method in a nitrogen atmosphere to produce powder.

First, a Pt capsule is filled with the first particle group. A silver brazing material is applied to the upper part of the crimped capsule, heat treatment is performed in a nitrogen or nitrogen-oxygen mixed gas atmosphere at a pressure of 0.1 MPa or more and 0.6 MPa or less, and the nitrogen or nitrogen-oxygen mixed gas is enclosed in the Pt capsule.

Next, the Pt capsule containing nitrogen or nitrogen oxygen is placed in the SUS capsule, and is heated at a pressure of 15 GPa or more and a temperature of 1500 ° C. or more with a general single-stage gunpowder gun impact compression device. Heat under pressure. Thereby, a powder having a cubic crystal structure can be synthesized from the first particle group. The pressure in the impact compression method is preferably 15 GPa or more and 50 GPa or less, more preferably 20 GPa or more and 40 GPa or less. The temperature in the impact compression method is preferably 1500° C. or higher and 3000° C. or lower, more preferably 2000° C. or higher and 2500° C. or lower.

The obtained powder is preferably pulverized to an average particle size of 0.1 μm or more and 10 μm or less using a ball mill or bead mill. A powder can be used as a raw material for a sintered body.

<Embodiment 4: Manufacturing method of sintered body>
A method for producing a sintered body according to an embodiment of the present disclosure includes a step of producing a powder (hereinafter also referred to as a “powder production step”) by the powder production method of Embodiment 3, and the powder A step of preparing the second particle group (hereinafter also referred to as a “second particle group preparation step”) and a step of sintering the second particle group to obtain a sintered body (also referred to as a “sintered body preparation step”) ).

(Powder production process)
In the powder production step, powder is produced using the powder production method described above. A specific method is the same as the powder manufacturing method of the third embodiment.

(Second particle group preparation step)
Next, a second particle group containing the powder obtained in the powder preparation step is prepared.

The second particle group can contain only powder, ie, 100% by volume of powder. The powder may also contain particles of one or both of binder compound particles and cubic boron nitride particles.

When the second particle group contains the binder compound particles, the content of the binder compound particles in the second particle group is preferably 0.5% by volume or more and 50% by volume or less, and 15% by volume or more and 45% by volume or less. is more preferable, and 30% by volume or more and 40% by volume or less is even more preferable. According to this, the wear resistance of the sintered body obtained by sintering the second particle group is improved.

When the second particle group contains cubic boron nitride particles, the content of the cubic boron nitride particles in the second particle group is preferably 10% by volume or more and 97% by volume or less, and 30% by volume or more and 65% by volume or less. is more preferable, and 45% by volume or more and 55% by volume or less is even more preferable. According to this, the wear resistance of the sintered body obtained by sintering the second particle group is improved.

When the second particle group contains one or both of the binder compound particles and the cubic boron nitride particles, it is preferable to mix the second particle group using a ball mill or a jet mill. The average particle size of the second particle group is preferably 0.1 μm or more and 10 μm or less.

(Sintered compact production process)
The second particle group is treated at a pressure of 10 GPa or more and 15 GPa or less and a temperature of 800° C. or more and 1900° C. or less to produce a sintered body. The sintered body preparation step is preferably performed in a non-oxidizing atmosphere, and particularly preferably in a vacuum or a nitrogen atmosphere. The sintering method is not particularly limited, but discharge plasma sintering (SPS), hot press, ultra-high pressure press, etc. can be used.

The obtained sintered body maintains the compounding ratio of each element in the second particle group.

EXAMPLES This embodiment will be described in more detail with reference to Examples. However, this embodiment is not limited by these examples.

[Example 1]
(Sample No. 102-104, 106, 107, 109-123)
<Preparation of first particle group>
Commercially available titanium nitride particles ("TiN-01" manufactured by Nippon New Metal Co., Ltd.), zirconium nitride particles ("ZrN-01" manufactured by Nippon New Metal Co., Ltd.), hafnium nitride particles (manufactured by Nippon New Metal Co., Ltd. "HfN-O ”), vanadium nitride particles (manufactured by Nippon New Metal Co., Ltd. “VN-O”), niobium nitride particles (manufactured by Nippon New Metal Co., Ltd. “NbN-O”), tantalum nitride particles (manufactured by Nippon New Metal Co., Ltd. “TaN- O”), chromium nitride particles (“Cr _NO ” manufactured by Nippon New Metal Co., Ltd.), aluminum particles (“#700F” manufactured by Minalco, indicated as “Al” in Table 1), silicon particles (Yamaishi Metal Co., Ltd. "No. 700" (manufactured by the company, indicated as "Si" in Table 1) is prepared in the amount described in the column "Type of first particle group raw material particles" in Table 1, and filled into a Pt capsule. A silver brazing material is applied to the upper part of the crimped capsule, and nitrogen heat treatment is performed at the pressure (0.1 MPa to 0.6 MPa) described in the column "Nitrogen pressure of nitrogen heat treatment" in Table 1, and nitrogen is enclosed in the Pt capsule. do.

<Powder preparation process>
Next, the nitrogen-encapsulated Pt capsule prepared above is placed in a SUS capsule, and subjected to impact compression at a target pressure of 30 GPa and a target temperature of 1500 ° C. with a general single-stage gunpowder gun impact compression device. to obtain a powder.

<Sintered compact manufacturing process>
The powder is recovered from the above Pt capsule and filled into another Pt capsule. This is sintered for 30 minutes under conditions of 7 GPa and 1500° C. in a belt type high pressure generator to obtain a sintered body.

(Sample No. 101)
Sample no. In 101, commercially available titanium nitride powder ("TiN-01" manufactured by Nippon New Metal Co., Ltd.) is prepared in the amount described in the column "Type of raw material particles of the first particle group" in Table 1, and this is made of Pt. A capsule is filled and sintered for 30 minutes under conditions of 7 GPa and 1500° C. in a belt type high pressure generator to obtain a sintered body.

(Sample Nos. 105 and 108)
Sample no. In 105 and 108, commercially available titanium nitride powder (“TiN-01” manufactured by Nippon New Metal Co., Ltd.) or zirconium nitride powder (“ZrN-01” manufactured by Nippon New Metal Co., Ltd.) was used. Prepared in the amount described in the column "Type of raw material particles in 1 particle group", using a diamond anvil, under the conditions of 18 GPa and 3073 ° C. in a nitrogen atmosphere, sintering for 15 minutes to obtain a sintered body. obtain.

<Analysis evaluation>
The powders obtained above (Sample No. 101 and No. 105 are commercially available titanium nitride powders, Sample No. 108 is zirconium nitride powder) and the sintered bodies were measured with an X-ray diffractometer. All powders and sintered bodies were confirmed to have a cubic crystal structure. Moreover, the powder and sintered body obtained above were measured with an X-ray diffractometer. The peak intensity ratio of each phase was consistent between the powder and the sintered body. That is, it was confirmed that the composition ratio of each element in the sintered body maintained the compounding ratio of each element in the powder.

For the powder obtained by pulverizing the sintered body obtained above, the atomic ratio of each metal element is analyzed by ICP emission spectrometry (device used: "ICPS-8100" manufactured by Shimadzu Corporation), and gas analysis measurement The atomic ratio of each non-metallic element was analyzed by the method (equipment used: "EMG950" manufactured by Horiba, Ltd.). A specific measuring method is the same as the method for measuring the atomic ratio of the metallic element in the powder and the atomic ratio of the non-metallic element in the powder in Embodiment 1, so the description thereof will not be repeated. In this example, since the first particle group contains only powder, the powder obtained by pulverizing the sintered body contains only the powder-derived material. The results are shown in the column of "sintered body (powder-derived material) analysis value" in Table 1. In addition, from the measurement results of the above powder and sintered body with an X-ray diffraction device, the atomic ratio of each metal element and the atomic ratio of each non-metal element in the sintered body are It was confirmed that the ratio and the atomic ratio of each non-metallic element were the same.

Using the atomic ratio of each metallic element and the atomic ratio of each nonmetallic element, the atomic ratio x1 of the metallic element and the atomic ratio y1 of the nonmetallic element are calculated, respectively, and using these, the atomic ratio x1 of the metallic element and A value of the ratio y1/x1 to the atomic ratio y1 of the nonmetallic element was calculated. The results are shown in the "y1/x1" column of Table 1.

<Cutting evaluation>
The resulting sintered body was cut with a laser for finish processing to prepare a cutting tool with tool model number DNGA150408. Using the obtained cutting tool, a cutting test of carburized hardened steel (SCM415H, hardness HRC60) was performed under the following cutting conditions to evaluate wear resistance.
Cutting speed: 300m/min.
Cutting depth: 0.15mm
Feed rate: 0.15mm/rev
Cutting oil: none The wear resistance of the cutting tool was evaluated by the following method. Cut 1 km under the above cutting conditions, observe the flank side of the cutting edge with an optical microscope, and measure the flank wear width. This cycle is repeated until the flank wear width reaches 0.2 mm, and the cutting distance at which the flank wear width reaches 0.2 mm is determined as the tool life. In practice, a straight line graph is drawn with the cutting distance on the horizontal axis and the flank wear width on the vertical axis, and the intersection of the 0.2 mm line on the vertical axis and the straight line graph is determined as the cutting distance. A longer cutting distance indicates better wear resistance.

The results are shown in the "cutting distance" column of Table 1.

<Results>
Sample no. The sintered body of No. 1 contains a powder-derived material made of TiN, and the value of the ratio y1/x1 between the atomic ratio x1 of the metallic element and the atomic ratio y1 of the non-metallic element in the powder-derived material is 1, and the comparison corresponds to the example.

Sample no. The sintered bodies of 102 to 123 contain a powder-derived material made of a nitride or oxynitride of Ti, Zr, Hf, V, Nb, Ta or Cr, and the value of "y1/x1" in the powder-derived material is greater than 1 and corresponds to the example.

Sample no. The tools manufactured using the sintered bodies of 102 to 123 are sample Nos. It was confirmed that the cutting distance was longer and the wear resistance was superior to that of the tool manufactured using the sintered body of No. 101.

[Example 2]
(Sample Nos. 201 to 245)
<Preparation of second particle group>
Sample No. obtained in Example 1; 103, 106, 109 powders, and commercially available titanium nitride (TiN) particles (“TiN-01” manufactured by Nippon New Metal Co., Ltd.), zirconium nitride (ZrN) particles (“ZrN-01” manufactured by Nippon New Metal Co., Ltd. ), vanadium nitride (VN) particles (“VN-O” manufactured by Nippon New Metal Co., Ltd.), niobium nitride (NbN) particles (“NbN-O” manufactured by Nippon New Metal Co., Ltd.), tantalum nitride (TaN) particles (Japan "TaN-O" manufactured by New Metals Co., Ltd.), chromium nitride (Cr _N ) particles ("Cr _N -O" manufactured by Nippon New Metals Co., Ltd.), tantalum carbide (TaC) particles (manufactured by Nippon New Metals Co., Ltd. " TaC”), titanium carbide (TiC) particles (“TiC-01” manufactured by Nippon New Metal Co., Ltd.), zirconium carbide (ZrC) particles (“ZrC-O” manufactured by Nippon New Metal Co., Ltd.), niobium carbide (NbC) particles (“NbC” manufactured by Nippon New Metal Co., Ltd.), vanadium carbide (VC) particles (“VC” manufactured by Nippon New Metal Co., Ltd.), and Al ₂ O ₃ particles (“TM-DAR” manufactured by Taimei Chemical Co., Ltd.). The second particle group (raw material particles for sintered body) is obtained by preparing at the mixing ratio described in the column of "Second particle group mixing ratio" and mixing with a planetary mill. Among these particles, particles other than powder correspond to raw materials of the binder compound.

<Sintered compact manufacturing process>
The above second particle group (Pt capsule is filled. This is sintered by a belt type high pressure generator under conditions of 7 GPa and 1500° C. for 30 minutes to obtain a sintered body.

<Analysis evaluation>
The second particle group and the sintered body obtained above were measured with an X-ray diffractometer. The peak intensity ratio of each phase was consistent between the second particle group and the sintered body. That is, it was confirmed that the composition ratio of each element in the sintered body maintained the compounding ratio of each element in the second particle group.

From the compounding ratio of each element in the second particle group, the atomic ratio x2 of the metallic element and the atomic ratio y2 of the nonmetallic element in the binder compound are calculated, and using these, the atomic ratio x2 of the metallic element and the atomic ratio of the nonmetallic element A value of the ratio x2/y2 to the atomic ratio y2 of the element was calculated. The results are shown in the "x2/y2" column of Table 2.

<Cutting evaluation>
Using the obtained sintered body, the same cutting tool as in Example 1 was produced, and under the same cutting conditions as in Example 1, the wear resistance was evaluated. The results are shown in the "cutting distance" column of Table 2.

<Results>
Sample no. The sintered bodies of 201 to 203 are powders containing TiN, ZrN or HfN ((y1/x1)>1), and nitrides or carbides of Ti, Zr, V, Nb, Ta or Cr, or Al ₂ O ₃ , with values of y1/x1 and x2/y2 greater than 1, corresponding to the examples. Sample no. The tools manufactured using the sintered bodies of 201 to 203 are sample No. 1 of Example 1. It was confirmed that the cutting distance was longer and the wear resistance was superior to that of the tool manufactured using the sintered body of No. 101 (corresponding to the comparative example).

[Example 3]
(Sample Nos. 301 to 323)
<Preparation of second particle group>
Sample No. obtained in Example 1; 103, 106, 109 powders, commercially available TiN particles, ZrN particles, VN particles, NbN particles, TaN particles, Cr ₂ N particles, TaC particles, TiC particles, ZrC particles, NbC particles, VC particles used in Example 2 , Al ₂ O ₃ particles, and cubic boron nitride (“FBN-AM 0-2” manufactured by Global Dia Co., Ltd.) were prepared at the compounding ratio described in the “2nd particle group compounding ratio” column of Table 3. , and mixed by a planetary mill to obtain a second particle group. Among these particles, particles other than powder and cubic boron nitride particles are raw material particles of the binder compound.

<Production of sintered body>
A capsule made of Pt is filled with the second particle group. This is sintered for 30 minutes under conditions of 7 GPa and 1500° C. in a belt type high pressure generator to obtain a sintered body.

<Analysis evaluation>
The second particle group and the sintered body obtained above were measured with an X-ray diffractometer. The peak intensity ratio of each phase was consistent between the second particle group and the sintered body. That is, it was confirmed that the composition ratio of each element in the sintered body maintained the compounding ratio of each element in the second particle group.

From the compounding ratio of each element in the second particle group, the atomic ratio x2 of the metallic element and the atomic ratio y2 of the nonmetallic element in the binder compound are calculated, and using these, the atomic ratio x2 of the metallic element and the atomic ratio of the nonmetallic element A value of the ratio x2/y2 to the atomic ratio y2 of the element was calculated. The results are shown in the "x2/y2" column of Table 3.

<Cutting evaluation>
Using the obtained sintered body, the same cutting tool as in Example 1 was produced, and under the same cutting conditions as in Example 1, the wear resistance was evaluated. The results are shown in the "cutting distance" column of Table 3.

<Results>
Sample no. Sintered bodies 301 to 323 comprise powders containing TiN, ZrN or HfN (y1/x1>1) and cubic boron nitride , and the value of y1/x1 is greater than 1 and correspond to examples. Sample no. The tools manufactured using the sintered bodies of 301 to 323 are sample No. 1 of Example 1. It was confirmed that the cutting distance was longer and the wear resistance was superior to that of the tool manufactured using the sintered body of No. 101.

Although the embodiments and examples of the present invention have been described as above, it is planned from the beginning that the configurations of the above-described embodiments and examples will be appropriately combined and variously modified.

The embodiments and examples disclosed this time are illustrative in all respects and should not be considered restrictive. The scope of the present invention is indicated by the scope of the claims rather than the above-described embodiments and examples, and is intended to include meanings equivalent to the scope of the claims and all modifications within the scope.

Claims (7)

A powder-derived material containing either or both of a nitride and an oxynitride of at least one first metal element selected from the group consisting of Group 4 elements, vanadium, tantalum and Group 6 elements of the periodic table with
The total content of the nitride and oxynitride of the first metal element in the powder-derived material is 90% by mass or more,
The content of the powder-derived material is 1% by volume or more,
In the powder-derived material, the ratio y1/x1 of the total atomic ratio x1 of the first metal element , aluminum and silicon to the total atomic ratio y1 of nitrogen and oxygen is greater than 1,
A sintered body, wherein the powder-derived material has a cubic crystal structure. Derived from a powder containing either or both of a nitride and an oxynitride of at least one first metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table equipped with materials,
The total content of the nitride and oxynitride of the first metal element in the powder-derived material is 90% by mass or more,
The content of the powder-derived material is 1% by volume or more,
In the powder-derived material, the ratio y1/x1 of the total atomic ratio x1 of the first metal element, aluminum and silicon to the total atomic ratio y1 of nitrogen and oxygen is greater than 1,
The powder-derived material has a cubic crystal structure,
Furthermore, at least one binder compound is contained in a total of 0.5% by volume or more and 50% by volume or less,
The binder compound contains at least one second metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table, and at least one of carbon, nitrogen and oxygen. consists of
A sintered body, wherein the ratio x2/y2 of the total atomic ratio x2 of the second metal element and aluminum to the total atomic ratio y2 of carbon, nitrogen and oxygen in the binder compound is 1 or more. 3. The sintered body according to claim 1, wherein the ratio y1/x1 is 1.1 or more and 1.3 or less. The sintered body according to any one of claims 1 to 3 , wherein the sintered body contains one or both of Al and Si. The sintered body further contains at least one binder compound in a total of 0.5% by volume or more and 50% by volume or less,
The binder compound contains at least one second metal element selected from the group consisting of Group 4 elements, Group 5 elements and Group 6 elements of the periodic table, and at least one of carbon, nitrogen and oxygen. consists of
2. The binder compound according to claim 1 , wherein the ratio x2/y2 of the total atomic ratio x2 of the second metal element and aluminum to the total atomic ratio y2 of carbon, nitrogen and oxygen is 1 or more. sintered body. 6. The sintered body according to claim 2 , wherein the value of said ratio x2/y2 is 1.04 or more and 1.06 or less. The sintered body according to any one of claims 1 to 6 , further comprising 10% by volume or more and 97% by volume or less of cubic boron nitride.